KR100515786B1 - Cellulosic networks with contaminant barriers or traps - Google Patents

Abstract

It is for a hard or semi-hard cellulose sheet having barrier or trap properties. The sheet consists of a randomly arranged cellulose fiber layer and a coating layer that acts as a barrier or trap against contaminants entering from the outside through the cellulose fiber layer. The layer contains an amount of cyclodextrin compound effective to absorb the permeate.

Description

Cellulosic nets with contaminant barriers or traps

FIELD OF THE INVENTION The present invention relates to improved hard or semi-rigid cellulosic packaging materials and to cellulosic packaging materials comprising chipboard, boxboard, paperboard or cardboard materials having permeable barrier or contaminant trapping or barrier properties. will be. Preferred barrier paperboard materials can prevent the permeable material from passing through the paperboard into the package contents from the surrounding atmosphere. In addition, mobile or volatile organic contaminants originating from cellulosic materials, printing chemicals, coating chemicals or recycled materials present in the paperboard may be trapped by the active barrier material in the paperboard.

The present invention encompasses various types of aspects including a barrier laminate structure having at least one layer of cellulose material having at least one barrier layer or a barrier polymer thin film layer containing an active barrier compound. Another aspect of the invention relates to food or edible material packaged with cellulosic packaging material with penetrant or contaminant barriers or traps. Another aspect of the present invention includes a method for packaging a material with a cellulosic network having a barrier or trap against contaminants or permeants to protect foods from inadequate taste, aroma and odor.

Non-woven_cellulosic materials, such as paperboard, boxboard, cardboard or chipboard, have a sheet material that is relatively thicker than paper, and the sheet material comprises small individual fiber-cellulose bonded to it. Made of fiber. Such fibers are generally bonded by secondary bonds, most preferably by hydrogen bonds. To form a cellulosic sheet, from a water suspension or dispersion on the fiber, a coarse mesh or sheet-like fiber is formed on a fine screen and then combined with a fiber additive, color tone, binder, second binder or other compound. Let's do it. After the sheet is formed on the elaborate screen, the rough sheet is dried, calendered and further processed into a finished sheet, which has a controlled thickness, improved surface condition, and has one or more coating layers, The amount of moisture is fixed. In addition, after sheet formation, the paperboard may be further coated, embossed or printed, and further processed before rolling and dispersing. The thickness of the paperboard, box board chipboard or cardboard is generally greater than about 0.25 mm. In general, paper is treated as a sheet material having a thickness of about 0.25 mm or less.

Non-woven cellulose fiber networks, such as paperboard, boxboard chipboard or cardboard, are made in various shapes and grades for a variety of applications. The finished paperboard is rough or smooth and can be laminated with other materials, but is generally thicker, heavier and less flexible than conventional paper materials. Paperboard can be made from the primary fiber source and the secondary or recycled fibrous material. The fibers used to make the paperboard come primarily from forest factories. Increasingly, however, paperboard is made of regenerated or secondary fibers obtained from paper, corrugated paperboard, woven or non-woven fibers, and similar fibrous cellulose materials. This recycled material potentially contains organic materials and other kinds of materials such as recycled inks, solvents, coatings, adhesives, and debris from materials that have been attached to the fiber source. Such organic matter has the potential to contaminate the contents in a container made of this recycled material.

The main components used in the manufacture of paper products are mechanical and semi-mechanical wood pulp, wood pulp of unbleached kraft compounds, white compound wood pulp, waste fibers, secondary fibers, nonwood fibers, woven or nonwoven recycled Fibers, wheelers and pigments. Various types of wood pulp are used, which are obtained from hard and soft wood. The chemical nature or composition of the paperboard is determined by the type of fiber used, or by the non-fiber material incorporated or acting on the surface of the paper during the paper making or subsequent paper conversion process. Paper properties that are directly affected by the chemical composition of the fiber include color, opacity, tensile, durability, and electrical properties.

In the manufacture of paperboards, barrier coatings are sometimes necessary to improve the resistance to water, vapor, oxygen, carbon dioxide, hydrogen sulfide, grease, fats, oils, fragrances or other miscellaneous compounds from passing through the paper material. . Known water (liquid) barriers can use sizing agents to vary the degree of wetness of the paper surface. A grease or oil barrier can be obtained by hydrating the cellulosic fibers to form a pinhole free sheet, or by coating a continuous thin film made of a material resistant to fat or grease on the paper. Gas or vapor barriers are formed by using a continuous thin film made of any material that can act as a barrier for a particular gas or vapor.

Various types of thin film materials have been developed as barriers to prevent the passage of steam, oxygen or other penetrating materials. Brugh Jr. U.S. Patent No. 3,802,984 to et al. Discloses a moisture barrier consisting of a stack of cellulosic sheets and thermoplastics. U. S. Patent No. 3,616, 010 to Dunn Bolter et al. Discloses a moisture barrier consisting of laminated corrugated paperboard and laminated thermoplastic bag stock. Brugh Jr. U. S. Patent No. 3,886, 017, et al., Discloses a moisture barrier in a container consisting of a laminated film of high density and low density cellulose sheets in a thermoplastic thin film. US Patent No. 3,972,467, filed by Willock et al, discloses an improved paperboard lamination for containers consisting of a lamination of a paperboard polymer thin film and an optional aluminum foil layer. US Patent No. 4,048,361, filed by Valyi, discloses a packaging comprising a gas barrier consisting of a stack of plastic cellulosic and other similar materials. U.S. Patent No. 4,698,246 to Gibens et al. Discloses lamination of paperboard polyester and other conventional components. U.S. Patent No. 4,525,396, filed by Ticassa et al., Discloses a pressure resistant paper container, which is a barrier having a gas barrier property prepared from a paperboard thermoplastic thin film, paper components and other conventional components. It consists of a laminated film of thin films. Cyclodextrin materials and cyclodextrin substitution materials are also known.

Other technologies associated with this application include Alan P., US Pat. No. 5,173,481, filed by Pitha et al., And Tetrahedron Reports 147, Department of Chemistry, Texas Tech University, Ludwig, Texas; USA, pages 1417-1474, October 4, 1982. Kroft et al. Also include "synthesis of chemically modified cyclodextrins." Pitha et al. Disclose cyclodextrins substituted with cyclodextrins. British patent application 0454910 A1 describes a method for coating a solid substitute with a polyisocyanate having a cyclolinked crosslinked. The primary use of cyclodextrin materials is to form a containing complex to move the containing compound to a desired location. Cyclodextrin materials have hydrophobic internal pores that are suitable for incorporating various organic components. Unmodified cyclodextrin containing complexes have been used in thin films as shown in Japanese Patent Application Nos. 63-237932 and 63-218063. As for the use of cyclodextrin-containing compounds, "Cyclodextrin Inclusion Compounds in Research and Industry", Willfrom Saenger, Angew. Chem. Int. Ed. Engl., Vol. 19, pp. 344-362 (1980). Cyclodextrin containing compounds are used in various types of vehicles. Materials may be delivered including deodorants, antibacterial materials, antistatic agents, edible oils, pesticides, fungicides, solubilizers, corrosion inhibitors, aroma amplifying compounds, pyrethroids, pharmaceutical and agricultural compounds, and the like. Such means are disclosed in a number of patents. Such patents include US Pat. Nos. 4,356,115, 4,636,343, 4,677,177, 4,681,934, 4,711,936, 4,722,815, and others, filed by Shibani et al. Japanese Patent No. 4-108523 filed by Yashimaga discloses a selective film for separating chiral compounds using a polyvinyl chloride thin film containing a large amount of substituted dextrin and plasticizer. In Japanese Patent No. 3-100065 filed by Yoshenaga, an unsubstituted cyclodextrin was used as a thin film layer. Nakazima, US Pat. No. 5,001,176, Bohr Jr. Many other US Pat. Nos. 5,177,129 and the like use cyclodextrins to act as composites for thin film stabilizing components. Zejtli et al., In US Pat. No. 4,357,468, disclose a particular example of the use of cyclodextrin materials as sulfites in separation techniques. This particular cyclonedextrin material is the polyoxalkylene substitution material used in the separation technique.

To date, many barrier materials have been proposed in the art, but to date no suitable material can function as a barrier against the many types of potential contaminants that can pass through the packaging material into the contents of the package. .

Thus, there is a need to develop new paperboard materials or laminates of original fibers, recycled fibers or mixtures thereof. The paperboard includes a barrier layer that can act as a barrier to the passage of contaminants and can also act as a trap for contaminants, when the contaminants are in the new material or when regenerating the fibers in paperboard fabrication. Is generated.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the size of uninduced cyclodextrin molecules, wherein α-, β-, and γ-cyclodextrins are shown.

It is known that the barrier properties of nonwoven cellulosic networks can be substantially improved with a barrier layer comprising a thin film containing an effective barrier of a predetermined amount of cyclodextrin. By forming a cellulose network with a barrier layer containing an effective penetrant or contaminant that absorbs the amount of cyclodextrin or a substituted or induced cyclodextrin compound, it reduces the passage of the penetrant through the cellulose network or the release of contaminant penetrant therefrom. I can prevent it. The cyclodextrin compounds used in this role are virtually free of cyclodextrin compounds-containing complex compounds, which serve as traps or barriers for the passage of penetrants or contaminants through the network or from the network into the container. The improved cellulosic network works by immobilizing a sufficient concentration of cyclonedextrin compound without the containing composite compound through the path of certain penetrants or contaminants passing through or exiting the cellulosic network. Cyclodextrin compounds that may be used in the present invention include unsubstituted cyclodextrins and cyclodextrins, which include substituents of the first and second hydroxyl groups which may be located in the cyclodextrin ring. This barrier layer can be corrugated with the cellulosic network or laminated in sheets on cellulose. In addition, the cyclodextrin material may be included in a coating compound that is coated on the surface or both sides of the cellulosic network after network formation. Such coatings may be formed from various types of networks, including injection coating, Rotogravure coating, and the like. In addition, the cyclodextrin material may be included in a thermoplastic thin film formed of one layer in a two-layer or multilayer laminate including cellulose. Such laminated films may include additional cellulosic material layers or other types of barrier layers. The laminate film may comprise an additional layer of thin film or trap material that may include a cyclodextrin barrier, and may optionally include other components. Cyclodextrins can be part of a thin film by injecting or coating a stretchable cyclodextrin layer within the thin film.

For the purposes of this specification, the term "net" means that non-oriented cellulose fibers are gathered like a sheet in a non-woven state. Such a network is usually a continuous network with virtually no gaps. Such nets take the form of thin paper sheets, heavy paper, cardboard, paperboard, cardstock or chipboard stocks or laminated films made of paper, paperboard, thermoplastic nets or sheets coated thereon.

For the purposes of this specification and claims, the term “penetrant” means a chemical compound or component that can be transported through a portion of a cellulosic network, under input with ambient temperature. Such penetrants can result from the ambient atmosphere or the environment and can be transported to be absorbed on one surface of the network and released through the interior of the cellulosic network to the opposite network surface. In addition, such penetrants can be generated from contaminants in the net or from components used in the manufacture and are released from the interior of the net to the surface of the net and released into the surrounding atmosphere or into a predetermined interior space encased in the net.

As used herein, the term "trap" refers to a cyclonedextrin or cyclonedextrin derivative that functions to absorb or prevent impurities from moving in the network caused by impurities present in the paper manufacturing process in the network. do. Such impurities arise from contaminants of cellulosic fibrous sources, for example contaminants resulting from regenerating used cellulosic material or from other sources. The term “barrier” means preventing the penetration of the penetrant from being released from one surface of the cellulosic network to the opposite surface of the network through the interior of the network.

Cellulose network

The paper or paperboard has a thin layered structure of non-oriented fibers bonded by hydrogen bonds. Paper or paperboard products are made of joinable fibrous material and form a layered structure of non-oriented fibers. Cellulosic fibers are the main material of paper manufacture, but certain paper or paperboard materials may include other fibers along with the cellulosic material.

Paper and paperboard are made from aqueous fiber suspensions. The cellulosic fibers are easily dispersed or suspended in water, which functions as a carrier before the suspension is applied to the screen during the paper manufacturing process. The main components of the fibrous material used in the manufacture of paperboards are wood pulp, waste paper such as newspapers, corrugated paperboard, deinked fibers, cotton, lint or pulp, and other materials. In addition, waste paper, known as secondary fibers, is becoming increasingly important in the manufacture of paper and paperboard. The percentage of recycled paperboard as a secondary fiber has increased significantly since 1980, making it a major fiber source. Cellulosic pulp, which is usually made from hard, soft wood, but can also be made from specially prepared cellulosic materials, is ground wood pulp, compressed ground wood pulp, ground wood pulp from chips (chips), refined mechanical Pulp, chemically refined mechanical pulp, chemical thermomechanical pulp, thermomechanical pulp, sodium sulfite treated TMP pulp, sulfonated chips and mechanical pulp, thermodynamic pulp in series. During these treatments, water, chemical additives and other materials to lower the elevated temperature are added to the chip wood to cut the wood into beneficial pulp material to make it smaller. When regenerating or pulping the secondary fibers, the fibers used are usually placed in a bath containing a variety of chemicals, which separate the cellulose components of the paper into the fibers and the ink coating in the recycled paper. Remove other materials.

Paper or paperboard is manufactured in a conventional paper processing process that can be processed continuously using a fourdrinier paper device. The pod linear paper apparatus typically includes a head box for making clean pulp, an initial screen for roller forming rollers, and a press connected with a pod linear screen for removing unnecessary water from the coarse web. The press adjusts the thickness and surface condition and finally the take-up reel or reservoir. During the podlinear treatment, the wet wood pulp enters the headbox and transports the ribbon wet wood into the pod linear water, which dilutes the thickness uniformly. The head box has a slice, which is a narrow opening in the head box through which the wood is carried on a wire mesh with a uniform thickness. The wire is a long belt made of woven fabric, initially a metal wire, but now usually made of plastic mesh. The wire runs along a series of rollers, which maintain the wire level and remove moisture from the coarse cellulose network. Water is first removed from the pulp by gravity, low pressure and finally by an absorber located under the wire. The paper net leaves the wire at this point. The continuous looped wire returns to the head box and carries another piece of wood. The coarse cellulose nets are press bonded by press means having a hard roller that presses the paper to remove moisture, thereby forming an approximate thickness. The cellulosic net then passes through a series of steam-filled drums called drying bins, where the remaining water evaporates. In the drying apparatus, chemicals may be added to the press which presses the surface of the net. Devices in the final finishing step include reel and rewinder rolls that compress the sheet, smooth the sheet, and control the final thickness. After this last step, the net is wound around the reel to be moved and used or further processed.

The dried paper net can be modified to improve its properties. Internal and external sizing can be used to check the water resistance. Wet strength agents and bonding additives may be used in the formation of the cellulosic network to assist in the retention of wet strength. Calendar processing can be used to physically modify the network. A calendar device is a pile of steel rolls that is placed in the final drying stage of a paper making device that crimps the net to form a flatter, smoother surface. This flat surface is printable, infused more smoothly when used in machinery, and can also be pigmented with a pigment coating. In general, pigment coatings require pigments and binders. Common pigments include clays, calcium carbonates, titanium dioxide, or plastic pigments. This pigment is generally applied as a finder or adhesive component in the form of a water-soluble suspension or dispersed colorant. Common binders or adhesives include starch, protein, styrene butadiene dispersion or lattice, polyvinyl acetate and lattice, acrylic lattice and the like. The coating treatment is a conventional coating device is used, the coating is uniformly applied to the entire surface, the degree of coating is determined by the appropriate thickness and amount to be applied to the entire network, and finally to create a smooth surface.

Cellulose network of the present invention is coated ground wood paper, coated paper, uncoated free sheet, writing paper, envelope stock, craft stock, non-stall board, tabulated card stock, unbleached packaging, Wrapping Whitening Color Stock, Bag and Color Stock, Unbleached Kraft Wrapping Stock, Wrapping Stock, Doping Stock, Waxing Stock, Hard Wood Pulp Paperboard, Unbleached Kraft Paperboard, Unbleached Linear Board, Heavy Mass Cup Stock And bleached paperboard stock, recycled paperboard, manufactured papers and boards, structurally insulated boards, and the like.

The paperboard of the present invention may also comprise corrugated paperboard material. Corrugated paperboard is usually made by making a single facer, which has a flute-shaped medium attached to the upper liner that makes a single facer-shaped board (one flat layer bonded to the wrinkled sheet). To produce a single phaser material, the net is first crimped and then the net is joined with the liner board using a commercially available corrugated starch adhesive. Once combined into a single phaser, the corrugated material and liner are bonded and dried. Once the single phaser is completed, it is bonded with the second liner using a similar corrugating adhesive. To make a double wall board or additional corrugated paperboard layer, a similar process is repeated until a sufficient number of layers are required for the desired application.

The paperboard and corrugated paperboard materials of the present invention can be used to make various types of packages. The folded package, including the corrugated container box and the folded cardboard, can be made from corrugated media, sodium bleached or unbleached paperboard. Flexible containers can be made from label items made of bags, colors, pouches, wrappers, and mesh thin films, or paper laminated films including foil clay coated paper laminates and thermoplastic coated paper laminates or multilayer paper laminates. have. Hard cylindrical containers can also be made by varying packaging needs such as shipping bottles and jars, cans and drums, and other containers. Containers can be used to transport food, powder, garden materials, hardware and virtual consumer or industrial goods that require robust packaging.

Cyclodextrin

The cellulosic networks of the present invention include cyclodextrins that are compatible and incorporated with thermoplastic polymers or substituted or derived cyclodextrins. In the present invention, commercial means by which the cyclodextrin material can be uniformly dispersed into cellulosic fibers or nets, have the ability to trap complex permeable materials or polymer impurities, and do not substantially reduce the important packaging properties of the net. May be present in the polymer. Compatibility can be determined by the properties of the network, such as tension, degree of tearing, penetration or penetration ratio of the penetrant, surface roughness, and the like.

Cyclodextrins are cyclic oligosaccharides consisting of at least 5, preferably at least 6 glucopyreynose units linked by α (1 → 4) bonds. Although cyclodextrins with up to 12 glucose residues are known, the most common homologs (α-cyclodextrins, β-cyclodextrins, γ-cyclodextrins) with 6, 7, and 8 residues are used. .

Cyclodextrins are produced by carefully selected enzyme synthesis. Cyclodextrins consist of 6, 7, or 8 glucose monomers arranged in toros or donut shaped rings, each represented by α, β, or γ cyclodextrins (see FIG. 1). By special binding of the glucose monomer, the cyclodextrin has a hard, one-ended, truncated conical molecular structure with an empty inside in a predetermined volume. Compared to the outside, the internal pores, which are lipophilic (friendly and hydrophobic with the hydrocarbon material in the water-soluble system), are the major structural features of the cyclodextrins, which are complex molecules (ie aromatic, alcohol, alkyl halides and aliphatic harleys). , Carboxylic acids and esters thereof, etc.). The complex molecule must at least partially meet the size that is bound in the inner pores of the cyclodextrin, resulting in the containing complex.

<Table> General Properties of Cyclodextrins

The oligosaccharide ring forms a torus that looks like a truncated cone, with the first hydroxyl group of each glucose residue on the torus of the torus. The second glucopyranose hydroxyl group is located on the end end. Parent cyclodextrin molecules and useful derivatives are represented by the following formula (ring carbon represents conventional numbers), and non-bonding represents the balance of the cyclic molecule.

R ₁ and R ₂ above are the first and second hydroxyl groups.

The cyclodextrin molecule reacts with the chemical reagent and reacts with the first hydroxyl group at position 6 and the second hydroxyl group at position 2 and 3. Because of the structure of the cyclodextrin molecule and the chemical reaction of the ring substituents, the reaction forces of all hydroxyl groups are not equal. However, under careful and effective reaction conditions, cyclodextrin molecules can be reacted to yield derivative molecules, which have all hydroxyl groups derived with a single substituent form. Such derivatives are cyclodextrins that are substituted each time. Cyclodextrins with selected substituents optionally substituted on only one or both second hydrogen groups or substituted only on the first hydrogen group are preferably synthesized. Moreover, direct synthesis of derived molecules with two different substituents or three different substituents is also possible. These substituents are directed to particular hydrogen groups or are placed randomly. For the purposes of the present invention, cyclodextrin molecules, when formed into clear thin films, sheets or solid structures, may be substituted with a substituent on the molecule to ensure that they are uniformly dispersed into the thermoplastic and do not impair the physical properties of the polymer. That is necessary to include sufficient thermoplastics. Apart from the introduction of substituents on the CD hydroxyl, other molecular modifications are possible. Other carbohydrate molecules can be incorporated into the cyclic backbone of the cyclodextrin molecule. The first hydroxyl group can be substituted using SN ₂ substitution, and the oxidized aldehyde or acid group can be formed for further reaction with an induction group or the like. The second hydroxyl group can be reacted and removed so that several known reactants remain that can add or cross double bonds to form inducible molecules. Furthermore, one or more ring oxygens of the glycan moiety are opened to generate reaction sites. This and other techniques are used to introduce compatible substituents to the cyclodextrin molecules.

Preferred diagrams for producing derived cyclodextrin materials having functional groups compatible with thermoplastic polymers include one or more reactions in the first or second hydroxyl group of the cyclodextrin molecule. Broadly, Applicants use a portion of a broad domain of subsubstitutes in the molecule. The derived cyclodextrin molecules include cyclodextrin esters such as acylated cyclodextrins, achelated cyclodextrins, tosylate, mesylates and other related sulfoderivatives, hydrocarbyl-amino cyclodextrins, alkylphosphonos and alkyl phosphates Earth cyclodextrins, pyridine substituted cyclodextrins, functional cyclodextrins containing hydrocarbyl sulfers, silicon-containing functional substituted cyclodextrins, carbonates and carbonates substituted cyclodextrins, carboxylic acids and related substituted cyclodextrins and others do. Some substituents should include regions that provide compatibility with the inducer.

Acyl groups are used to commercialize functional groups including acetyl, propionyl, butyryl, trifluoroacetyl, benzoyl, acryloyl, and other well known groups. Acylation reactions can be carried out using suitable anhydrides, acid chlorides and known protocols. Peroxylated cyclodextrins can be made. In addition, cyclodextrins having up to all available hydroxyl groups substituted by such groups can be made by the combination of available hydroxyl groups substituted by one or two or more other functional groups.

Cyclodextrin materials may also be reacted with alkylating agents to produce alkylated cyclodextrins. Alkylated groups can be used to produce peralkylated cyclodextrins using sufficient reaction conditions to react available hydroxyl groups with an alkylating agent. In addition, depending on the alkylating agent and the cyclodextrin molecules used in the reaction conditions, cyclodextrins substituted with up to all available hydroxyl groups can be produced. Typical examples of alkyl groups useful for forming alkylating agent cyclodextrins include methyl, propyl, benzyl, isopropyl, tert (t) -butyl, allyl, trityl, alkyl-benzyl, and other common alkyl groups. Such alkyl groups can be made using conventional methods such as reacting hydroxyl groups with halogenated alkyl or alkylated alkylsulfate reactants under appropriate conditions.

Tosyl (4-methylbenzene sulfonyl), mesyl (methane sulfonyl) or other related aryl sulfonyl or aryl forming reagents can be used to prepare compatible cyclodextrin molecules for use in thermoplastics.

The primary -OH group of the cyclodextrin molecule reacts better than the secondary group. However, the molecules can be substituted at almost any position to form a useful composition.

Such sulfonyls containing functional groups can be used in derivatives of either the primary hydroxyl group or the secondary hydroxyl group of any glucose component of the cyclodextrin molecule. The reaction can be carried out using a sulfonyl chloride reactant which can effectively react with either primary or secondary hydroxyl groups. Sulfonyl chloride is used in the appropriate molar ratio depending on the number of target hydroxyl groups in the molecule requiring substitution. Symmetric (per compound substituted by a single sulfonyl component) or asymmetric (primary and secondary hydroxyl groups substituted by a mixture of groups containing sulfonyl derivatives) can be prepared using known reaction conditions. have. Sulfonyl groups can generally be combined by acyl or alkyl groups as selected by the experimenter. Finally, monosubstituted cyclodextrins can be made and the single glucose component inside the ring contains between one and three sulfonyl substituents. The balance of the cyclodextrin molecule remains unreacted.

Amino and other azido derivatives of cyclodextrins with pendant thermoplastic polymers comprising moieties can be used in the containers, sheets or thin films of the present invention. Sulfonyl derived cyclodextrin molecules are used to generate amino derivatives from cyclodextrin molecules substituted with sulfonyl groups via nucleophilic displacement with sulfate groups by azide (N ₃ ^-1 ) ions. Can be. Azido derivatives are subsequently converted to substituted amino compounds by reduction. A large number of these azido or amino cyclodextrin derivatives have been prepared. Such derivatives can be prepared from symmetrically substituted amine groups (derivatives having two or more amino or azido groups symmetrically arranged on a cyclodextrin backbone or symmetrically substituted amine or azide derivatization Derivatives as cyclodextrin molecules). By nucleophilic substitution reactions that produce nitrogen containing groups, the primary hydroxyl group at the 6-carbon atom is the position at which the nitrogen containing group is introduced. Examples of nitrogen-containing groups that may be useful in the present invention are alkyl including acetylamino group (-NHAc), methylamino, ethylamino, butylamino, isobutylamino, isopropylamino, hexylamino and other alkylamino substituents. Amino. Amino or alkylamino substituents may be further reacted with other compounds that react with nitrogen atoms to further derivatize the amine groups. Other possible nitrogenous substituents, including halogenated derivatives of cyclodextrins, quaternary substituted alkyl or aryl ammonium chloride substituents, dialkylamino such as dimethylamino, diethylamino, piperidino, piperizino Can be prepared as a feedstock for the preparation of cyclodextrin molecules substituted with compatible derivatives. In such compounds the primary or secondary hydroxyl groups are substituted by halogen groups such as fluoro, chloro, bromo, iodo or other substituents. The most suitable position for halogen substitution is the primary hydroxyl at 6-position.

Hydrocarbyl substituted phosphono or hydrocarbyl substituted phosphato groups can be used to derive compatible derivatives on cyclodextrins. In the first hydroxyl, the cyclodextrin molecule can be substituted with alkyl phosphato, aryl phosphato groups. Alkyl phosphato groups can be used to branch the second and third hydroxyls.

Cyclodextrin molecules are substitutable with heterocyclic nuclies comprising pendant imidazoles, histidines, imidazoles, pyridinos and substituted pyridinos.

Cyclodextrin derivatives may be modified to have sulfur-containing functional groups so that substituents are compatible on the cyclodextrin. Unlike the aforementioned sulfonyl acylate groups, sulfur-containing groups prepared based on sulfhydryl formulas can be used to induce cyclodextrins. Such sulfur-containing groups include methylthio (-SMe), propylthio (-SPr), thi-butylthio (-SC (CH ₃ ) ₃ ), hydroxyethylthio (-S-CH ₂ CH ₂ OH), imida Zolylmethylthio, phenylthio, substituted phenylthio, aminoalkylthio, and the like. Based on the ethers or thioethers described above, cyclodextrins with substituents ending in carboxylic acid functional or hydroxyl aldehyde ketones can be prepared. Such groups include hydroxylethyl, 3-hydroxypropyl, methyllooxylethyl and the corresponding oxime isomers, formyl methyl and its oxime isomers, carbylmethoxy (-O-CH ₂ -CO ₂ H), car Bilmethoxymethyl ester (-O-CH ₂ CO ₂ -CH ₃ ). Cyclodextrins with derivatives formed using silicone formulas may contain compatible functional groups.

Cyclodextrin derivatives with functional groups comprising silicones are prepared. Generally, a silicon group means a group having a silicon atom once substituted or a silicon-oxygen backbone group repeatedly connected to a substituent. Typically, a significant amount of silicon atoms in the silicone substituents contain hydrocarbyl (alkyl or aryl) substituents. Silicon substitution molecules generally have increased thermal and oxidative stability and chemical inertia. In addition, the silicon group has increased weather resistance, enhanced insulation, and increased surface tension. The molecular structure of a silicon group is because the silicon group can have one silicon atom or two to twelve silicon atoms in a small amount of silicon (which may be linear or branched and contain a number of repetitive silicon-oxygen groups). It may vary and may be substituted with various kinds of functional groups. For the purposes of the present invention, simple silicones containing small amounts of substituents are preferred, such as trimethylsilyl, mixed methyl-phenyl silyl groups, and the like. The desired βCD and acetylated and hydroxy alkyl derivatives can be obtained from American Maize-Products Co., Corn Processing Division, Hammond, IN.

pellicle

The barrier packaging material may be in the form of coated cellulose nets or cellulose net / thin laminates. The cyclodextrin may be a network, a thin film, or a portion thereof. The thin film or sheet is an unsupported flat part made of thermoplastic resin, and its thickness is much smaller than its width or length. Thin films are usually considered to be 0.25 mm or less and usually have a thickness of 0.01 to 20 mm. The sheet ranges from approximately 0.25 mm to several cm, with a typical thickness of 0.3 to 3 mm. The thin film or sheet may be laminated and combined with other sheets and structural units. Important features include tension, tensile force, strength, tearing, optical properties including turbidity, transparency, chemical repulsive forces such as absorption and penetration of various types of penetrants, including vapor and other infiltrations, and electrical properties such as dielectric constants. Properties, shrinkage, cracking and durability.

Thermoplastics can be formed in the barrier thin film by various processes such as injection of hollow thermoplastics, linear biaxial thin film injection and dispersion of molten thermoplastic, monomer or polymer (aqueous solution or organic solvent). These methods are known manufacturing processes. The polymer thermoplastics that lead to successful barrier thin film formation are: Experienced technicians in the manufacture of thermoplastics know how to handle polymer materials during the thermoplastic process and how to terminate their use by controlling the molecular mass (melting index is a measure of molecular mass in the thermoplastic industry. Melting index is inversely proportional to molecular mass, density, and latticeness). Polypropylene, nylon, nitrile, PETG and polycarbonate are often used to make hollow thin films, but polyapa such as hollow thermoplastic injection polyolefins (LDPE (low density polyethylene), LLDPE (linear low density polyethylene), HDPE (high density polyethylene) Olefins) are frequently used thermoplastic polymers. Typically the polymer has a melt index of 0.2 to 3 grams / 10 minutes, a density of about 0.910 to 0.940 grams / cc, and a molecular mass (Mw) in the range of about 200,000 to 500,000. In biaxially oriented thin film injection, the most frequently used polymer is an olefin base, usually polyethylene and polypropylene (melting index ranges from 0.1 to 4 grams / 10 minutes, preferred range is 0.4 to 4 grams / 10 minutes, molecular mass (Mw ) Is about 200,000 to 600,000). Polyester and nylon cans can also be used. In casting, the molten thermoplastic or monomer dispersion is usually produced from polyethylene or polypropylene. Occasionally nylon, polyester and PVC are cast. In roll coatings such as water soluble acrylics, urethanes and PVDCs, the dispersion is polymerized to optimum crystals and molecular mass before coating.

Various types of thermoplastics are used to make thin film and sheet products. Such materials include poly (acrylonitrile-co-butadiene-co-styrene) polymers, acrylic polymers such as polymethylmethacrylate, poly-ene-butyl acrylate, poly (ethylene-co-acrylic acid), poly ( Ethylene-co-methacrylate) and the like; Cellophane, cellulosic including cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate and the like; Fluoropolymers containing polytetrafluoroethylene (teflon), poly (ethylene-co-tetrafluoroethylene) copolymers, (tetrafluoroethylene-co-propylene) copolymers, polyvinyl fluoride polymers and the like Polyamides such as 6, nylon-6,6; Polycarbonate; Polyesters such as poly (ethylene-co-tetraphthalate), poly (ethylene-co-1, 4-naphthalene dicarboxylate), poly (butylene-co-terephthalate); Polyamide materials; Polyethylene materials, including low density polyethylene; Linear low density polyethylene, high density polyethylene, high molecular weight high density polyethylene and the like; Polypropylene, biaxially oriented polypropylene; Polystyrene, biaxial polystyrene, thin vinyl film containing polyvinyl chloride, (vinyl chloride-co-vinyl acetate) copolymer, polyvinylidene chloride, polyvinyl alcohol, (vinyl chloride-co-vinylidene dichloride) copolymer, Special thin films containing polysulfone, polyethylene sulfide, polyphenylene oxide, liquid crystalline polyester, polyether ketone, polyvinyl butyral and the like.

Conventional thermal lamination techniques can be used to laminate thermoplastic thin film materials to a cellulose network. In this technique, two general-purpose methods can be used to bond thin films to cellulose network substrates. This thin film can be directly injected into the network of cellulose by conventional heat treatment techniques and bonded with the network. In the injection coating process, the plastic pellets containing the cyclodextrin derivatives are melted at a high temperature (usually 350 ° C. or higher). Molten plastic is injected through narrow slits or dies. At this time, the molten material comes into contact with the cellulose network. It is immediately pressed by a very chilled and conditionally cold chill roll (30-40 ° C.). This operation not only forms a strong laminate bond to the cellulose network, but also smooths the plastic with an impermeable surface. The appearance and nature of the coating usually depends on the form of the chill roll used and is independent of the properties of the plastic material.

In addition, a thin film may be obtained by a thin film rolling operation, and the thin film may be laminated on a cellulose network using a heating technique or a bonding layer which is usually activated by heating. The rolled or already cast thin film can be obtained by contacting a cellulosic net, heated at a temperature above its melting point and immediately pressed into a smooth, cold chill roll. This lamination process is usually performed by the above-mentioned well-known process. Such lamination can be improved by using an adhesive to help form a bonded thin film lamination. Such materials are usually coated onto thin films or cellulosic nets before heat treatment.

Cellulosic networks or similar structured cellulosic layers may be coated with a liquid coating compound comprising an effective amount of cyclodextrin or substituted cyclodextrin to incorporate the cyclodextrin material into the barrier cellulosic network. Such coating compounds are usually formed using liquid materials. Liquid materials include water-soluble materials and organic solvents. Water-soluble materials are usually formed by mixing additives or ingredients with water which can form useful coatable aqueous dispersions. Solvent dispersions for organic solvents can be made using corresponding known solvent group coating techniques.

In forming the barrier layer of the present invention, it may be coated on a later laminated thin film on a cellulose network or coated to form a thin film on a cellulose network. This coating process involves applying a liquid to the moving cellulosic net. The coating process generally uses a device having a coating device and a measuring device. By carefully controlling the amount and thickness of the coating material, an optimal barrier layer can be obtained without consuming material. Many coating machines include, but are not limited to, stress sensitive coaters such as measuring rods, stations capable of maintaining the coating weight as the net tension changes, coaters using brush coating methods, and air knives. Things like air knife coaters are well known. The coating machines can be used to coat one or both sides of a flexible thin film, or one or both sides of a cellulose network.

The coating machines described above generally maintain a coating component in accordance with an effective amount of cyclodextrin or substituted cyclodextrin material, and apply liquid components including additives and thin film forming materials to assist in the formation. The thin film forming material is often called a binder. The binder is a high molecular weight polymer and is present at the time of final coating. Thermoplastic polymers or crosslinked polymers may be used. The binder is gathered into certain overlapping classes including acrylics, vinyls, alkyls, polyesters and the like. Moreover, the components described above are materials that can be used when forming polymer thin films with corresponding materials used in the formation of water-soluble and solvent-based coating components. The coating components can be made by mixing a liquid medium with a solid material comprising a polymer, cyclodextrin and various useful additives. Generally, cyclodextrin materials are added to the coating component as part of the solid component. The solids present in the coating components comprise about 0.01-10 wt% of the cyclodextrin compound, preferably about 0.1-5 wt%, most preferably cyclo to the total solids amount in the solvent-based dispersion component. 0.1-2 wt% of dextrin material.

Packaged and packaged goods

Cellulose networks comprising cyclodextrins or compatible derived cyclodextrin containing complexes can be used in a variety of packaging formats to package a variety of items. General packaging ideas can be used. For example, items can be fully packaged in pouches, bags, and so on. It is also possible to use a net as a paper cover on a rigid plastic container. Such containers may have rectangular, circular, rectangular or other shaped cross sections and flat bottoms and open tops. Containers and paper or mesh lids can be made from the materials of the present invention coated or laminated with thermoplastics. In addition, the materials of the invention coated or laminated with thermoplastics can be used to form bubble pack packages, clam shell shaped facades, tubes, trays, and the like. Products that can be packaged by the method of the present invention include coffee, ready-to-eat cereals, frozen pizzas, cocoa or other chocolate products, dried mixed graves and soups, snack foods (chips, crackers, popcorn, etc.), baked goods Food, pastries, breads, dried pet foods (such as cat food), butter or buttery notes, meat, especially butter or buttery notes used in the manufacture of microwave popcorn in microwaveable paper containers, fruit and Nuts, etc.

The nature of the above-described coating or preparation for the production of cyclodextrin derivatives, thermoplastic thin films, thin film coatings and nets, and the processing of cyclodextrins for making compatible derivatives is due to the structure of paper cyclodextrins or barriers for compatible cyclodextrins or barriers in cellulose networks. Provide a basis for understanding the technique of merging. The following examples of thin film preparation and penetration data provide a better understanding of the present invention and include the best mode.

After this work of producing derivatives of cyclodextrins and mixing cyclodextrins in thermoplastic thin films, we have found that cyclodextrins can be easily induced using various known chemical protocols. The cyclodextrin material is melt mixed in the thermoplastic material and can inject pure thermoplastic material with the cyclodextrin material uniformly dispersed throughout the thermoplastic material. It has also been found that cyclodextrin derivatives can be combined with various types of thermoplastic thin films. Cyclodextrin materials can be incorporated into thin films over a wide range of concentrations. Cyclodextrins containing thermoplastic mouldings can be hollow into thin films of various thicknesses, can be hollow that can not be melted and crushed, and can be variations of other thin films or sheets. It has also been found that barrier layers can be formed from polymer dispersions containing cyclodextrins. From our experiments, cyclodextrin induction techniques could be used to reduce the barrier properties, namely the delivery ratios of aromatic hydrocarbons, aliphatic hydrocarbons, ethanol and steam. It has also been found that the use of cyclodextrin materials improves the surface properties of thin films. The surface tension of the thin film and the electrical properties of the surface were also improved. This result increases the usefulness of the thin film of the present invention in coating, printing, radiating, handling and the like. In our first work, we found:

(1) It has been found that several modified cyclodextrin candidates are compatible with LLDPE resins, providing a complex of remaining volatile contaminants of LLDPE as well as reducing organic permeates that diffuse through the thin film. (2) Unmodified βCD adversely affects the transparency, thermal stability, machinability, and barrier properties of the thin film. In contrast, selected modified βCDs (acetylated and trimethylsilyl ether derivatives) do not affect clarity and thermal stability. The injected plastic material is somewhat damaged on the surface by the mechanical workability and thus reduces the barrier property of the thin film. (3) thin films comprising modified βCD complexes reduce aromatic permeate by 35% at 72 ° F. (22.22 ° C.) and 38% at 105 ° F. (40.56 ° C.); Aliphatic permeate decreased to only 9% at 72 ° F. (22.22 ° C.). These results will be greatly improved if the self-life test conditions are not used in the worst case to test the thin film. (4) The complex ratios differ for aromatic and aliphatic infiltrates. The thin film containing the modified βCD has a better compound ratio of aromatic (gasoline type compound) than aliphatic (print ink type compound). In contrast, the composite ratio of the thin film coating is better for aliphatic compounds than for aromatic compounds. (5) βCD containing an acrylic coating can reduce aliphatic permeate by 46% to 88%, while aromatics are reduced by 29%.

Qualitative Manufacturing

For the first time, four experimental test thin films are produced. Three of the thin films contain β-cyclodextrin loaded with 1%, 3% and 5% (wt./wt.), And the fourth thin film has no βCD and is made from the same amount of resin and additives. to be. 5% loaded βCD thin films were tested for complexes of residual organics in the test thin films. Although βCD was found to effectively synthesize residual organics in linear low density polyethylene (LLDPE) resins, it could not be combined with the resin and the aggregated βCD particle mass.

Nine modified and pulverized βcyclodextrins (particle size 5 to 20 microns-ie 50,000 to 200,000 mm 3) were evaluated. The different cyclodextrin variants are acetylated, octanyl succinate, ethoxyhexyl glycidyl ether, quaternary amine, tertiary amine ), Carboxymethyl, succinylated, amphoteric and trimethylsilyl ether. Each experimental cyclodextrin (1% loading wt / wt) was mixed with low density polyethylene (LLDPE) using a Littleford mixer and injected using a double screw Brabender injection machine.

The nine modified cyclodextrin and powdered cyclodextrin LLDPE profiles were examined by optical microscope at magnifications of 50X and 200X. The microscope test was used to visually check the compatibility between the LLDPE resin and the cyclodextrin. Three of the ten cyclodextrin backbones tested (acetylated, octanyl cyclinate, and trimethylsilyl ether) were found to be compatible with LLDPE resins.

The remaining thin film volatiles synthesized were cryotrapping to test three injected profiles containing βCD thin film samples and 1% (wt / wt) of acetylated βCD octanyl cyclinate βCD and trimethylsilyl ether. It was measured using the cryotrapping procedure. The method consists of three separate processes. The first two steps are performed simultaneously, but the third, metrological technique for separating and detecting volatile organic compounds, is performed after the first and second steps. In the first step, an inert purified dry gas is used to remove volatiles from the sample. During the degassing step, the sample is heated at 120 ° C. The sample is reacted by surrogate (benzene-d6) just prior to analysis. Benzene-d6 serves as an internal QC surrogate to calibrate each test data set for reinstatement. The second step concentrates the volatiles removed from the sample on top of the vial vessel immersed in the liquid nitrogen trap by cooling the compound from the removal gas. At the end of the degassing step, an internal standard (toluene-d8) is injected directly onto the vial and the bottle is immediately capped. Method and System Blanks are treated in the same manner as the sample to intersect with the sample and monitor for contamination. The concentrated organic components are then separated, identified and weighed by heated superspace high resolution gas chromatography / mass spectrometry (HRGC / MS).

Residual volatiles analysis results are shown in the table below.

<Table 1>

In these preliminary qualification experiments, the βCD derivatives have been shown to effectively synthesize trace volatile organics inherent in low density polyethylene resins. In LLDPE thin films loaded with 5% βCD, about 80% of organic volatiles were synthesized. However, all βCD thin films (1% and 5%) were colorless (light brown) and odorless. The problem of color and fragrance is believed to be the result of the direct degradation of the CD or the impurities in the CD. Two odor-active compounds (2-furaldehyde and 2-furanmethanol) were identified in the thin film.

Among three modified compatible CD candidates (acetylated, octanyl cyclinate, and trimethylsilyl ether), acetylated and trimethylsilyl ether CD have been shown to effectively synthesize trace volatile organics inherent in low density polyethylene resins. . 1% loading of acetylated and trimethylsilyl ether (TMSE) βCD was shown to synthesize about 50% residual LLDPE organic volatiles, but octanyl circinate CD did not synthesize LLDPE resin volatiles. Powdered βCD appeared to be less effective (28%) than acetylated and TMSE modified βCDs.

All plastic packaging materials interact to some extent with the food they protect. The method of interaction of plastic packaging of food is by the movement of organic molecules from the surroundings through the polymer thin film into the upper space of the packaging. The transport or transfer of organic molecules to food during storage is influenced by ambient conditions such as temperature, storage time and other factors (eg moisture, type and concentration of organic molecules). This shift can be related to quality and toxicological effects. The purpose of a packaged thin film test is to determine how a particular barrier can affect the quality of an individual food packaged. For a hypothetical accelerated shelf-life test for low moisture food production, the test was conducted at a temperature of 72 ° F. (22.22 ° C.) and a temperature of 105 ° F. (40.56 ° C.) and a relative humidity of 60%. Was done. These temperature and humidity conditions were similar to those of uncontrolled warehouses and depots.

If the polymer is moisture sensitive, relative humidity can affect the behavior of the thin film, especially in low moisture foods. Since the packaging membrane would separate two humidity extremes in actual end-use conditions, the relative humidity of the penetration device was controlled on both sides of the membrane. The peripheral side representing the outer surface of the package was maintained at 60% relative humidity, and the side of the sample representing the interior of the package containing the low moisture activity food was maintained at 0.25%.

Combinations of penetrants were used to measure the function and action of the CD. The combination was practically used since gasoline (mainly aromatic hydrocarbon mixtures) and printing ink solvents (mainly aliphatic hydrocarbon compounds) were formed from the mixing of compounds rather than from a single compound.

Aromatic permeates included ethanol (20 ppm), toluene (3 ppm), p-xylene (2 ppm), o-xylene (1 ppm), trimethyl-benzene (0.5 ppm) and naphthalene (0.5 ppm). An aliphatic permeate, ie, a commercially available colored solvent mixture containing about 20 compounds, contained 20 ppm. Penetration testing equipment consists of two penetration cells or flasks with 1200 ml holes (in the outer cell or feed side) and 300 ml holes (in the sample cell or penetration side).

Experimental thin films were measured using a closed-volume permeation device mf. Changes in total penetration concentration as a function of time were measured using high resolution gas chromatography (HRGC) operated with a frame ionization detector (FID). Compound concentrations on the sample side (food side) were calculated from the reaction factors of each compound. Concentrations were reported in parts per million (ppm) in volume / volume ratio. The total penetration concentration in the sample plane of the thin film is shown as a function of time.

For the experiment, four experimental test thin films were made. The three thin films contained 1%, 3% and 5% of βCD, respectively, and the fourth thin film was a control sample, which contained the same amount of resin and ancillary materials, but did not add βCD alone.

In addition, as a second experiment, a second experiment was performed to determine whether adding βCD between two control films affects organic vapor infiltration. The experiment was performed by lightly spraying βCD between two control thin sheets.

According to the experimental results, the control thin film showed better performance than the thin film to which βCD was added. In addition, it was shown that the higher the βCD value, the poorer the film's function as a barrier.

Experimental results with the βCD sandwiched between the two control films showed that the addition of βCD was twice as effective in reducing the penetration vapor as the control sample without βCD. From these experiments, it can be seen that if the barrier properties of the thin film do not change during the manufacturing process, which makes the thin film a less effective barrier, the CD forms a complex with the penetrating organic vapor in the thin film.

In removing the aromatic permeate at 72 ° F. (22.22 ° C.), the 1% TMSE βCD thin film (26%) performed slightly better than the 1% acetylated βCD thin film (24%). For the aromatic permeate at 105 ° F. (40.56 ° C.), both 1% TMSE βCD and 1% acetylated βCD were 13% more effective at removing the aromatic permeate than 72 ° F. (22.22 ° C.).

In addition, in the removal of directional permeate, the 1% TMSE thin film (36%) performed better than the 1% acetylated thin film (31%).

In the removal of aliphatic permeate, at 72 ° F. (22.22 ° C.), the 1% TMSE thin film was more effective than 1% acetylated βCD at first. However, 1% TMSE βCD was poor compared to the control sample, and the removal rate of aliphatic penetrant of 1% acetylated βCD was only 6%.

The experimenters prepared two experimental aqueous coating solutions. One solution contained hydroxyethyl βCD (35% by weight) and the other solution contained hydroxypropyl βCD (35% by weight). Both solutions contained 10% acrylic emulsion comprising a polyacrylic acid dispersant (Polysciences, Inc.) having a molecular weight of about 150,000 as a thin film forming adhesive (15% solids by weight). Test thin film samples were manually coated by stacking two LLDPE thin films with these solutions. At this time, two different coating techniques were used. The first technique scraped the two sample surfaces slightly, coated them with a hand-roller, and laminated the thin films. Rev. One sample did not scratch in the lamination process. A vacuum thin film process was performed on all coated samples to remove air bubbles between the thin film sheets. The thin film coating thickness was about 0.005 inches. The CD coated thin film and the hydroxymethyl cellulose coated control thin film were tested in this order.

In terms of aromatic and aliphatic vapor reduction, hydroxyethyl βCD coated performance was good during the first few hours of exposure to steam, but gradually decreased after 20 hours of testing. The hydroxyethyl βCD coating showed a higher removal effect on aliphatic vapors than aromatic vapors. This is presumed to be due to the difference in molecular weight (ie, aliphatic compounds have a lower molecular weight than aromatic compounds). After 20 hours of testing, the reduction in aliphatic permeate was 46% based on the control sample. After 17 hours of testing, the reduction in aromatic vapor was 29%, based on the control sample.

The Rev. 1 coated hydroxyethyl βCD had a 87% reduction in aliphatic permeate after 20 hours based on the control sample. It is unknown whether the amount of vapor reduction of about 41% more effective than the hydroxyethyl βCD coated thin film when scratching the sample surface is due to the method of coating the thin film.

The hydroxyethyl βCD coating (29%) had slightly higher aromatic permeate removal at 72 ° F. (22.22 ° C.) compared to hydroxypropyl βCD coating (20%). Such coated thin films are useful for laminating to cellulose nets to form the barrier layer of the present invention.

Large scale thin film experiment

Preparation of Cyclodextrin Derivatives

Acetylated β-cyclodextrins with 3.4 acetyl groups bound to the first -OH group position of each cyclodextrin were obtained.

Experimental Example II

Trimethyl silyl ether of β-cyclodextrin

3 L of dimethylformamide was placed in a rotary still equipped with 4000 ml round bottom flask in a nitrogen atmosphere where N ₂ was injected at a rate of 100 ml per minute. To dimethylformamide was added 750 g of β-cyclodextrin. The solution was stirred at 60 ° C. to dissolve β-cyclodextrin in dimethylformamide. After dissolution, the flask was removed from the rotary distiller and the contents were cooled to about 18 ° C. The flask was placed on a magnetic stirrer equipped with a steer rod, 295 ml of hexamethyldisilazine (HMDS: Pierce Chemical No. 84769) was added to the flask, followed by 97 ml of trimethylchlorosilane (TMCS: Pierce Chemical). No. 88531) was carefully added. At this time, the meaning of adding carefully reacts by adding an initial amount of 20ml, and proceeds until the addition is completed by adding an additional 20ml after the reaction. After complete addition of the TMCS and completion of the precipitation reaction, the flask and its contents are placed in a rotary distiller heated to 60 ° C. while maintaining an inert nitrogen atmosphere by flowing N ₂ at 100 ml / min. After the reaction proceeds for 4 hours, the solvent is removed and 308 g of dried material is obtained. After filtering the material, the filtrate was washed with deionized water to obtain a silylated product, dried in a vacuum oven (from 0.3 inch Hg to 75 ° C.) to obtain a powdered material and then compounded with thermoplastics. Store for bonding. Looking at the spectra for the material, it can be seen that about 1.7 trimethylsilylether substituents were formed for each β-cyclodextrin molecule. Substitution mainly occurs at the primary 6-carbon position.

Experimental Example III

Hydroxypropyl β-cyclodextrin with 1.5 hydroxypropyl groups substituted for each molecule at the position of the primary 6-OH group of βCD was obtained.

Experimental Example IV

Hydroxyethyl β-cyclodextrin was obtained in which 1.5 hydroxyethyl groups were substituted for each molecule at the position of the primary 6-OH group of βCD.

Manufacture of thin film

A series of thin films were prepared using low density polyethylene resins, βCDs, and βCD derivatives such as acetylated derivatives or trimethylsilyl derivatives of β-cyclodextrins. The polymer particles were dry mixed with powder β-cyclodextrin and β-cyclodextrin derivative, fluoropolymer lubricant (3M), and antioxidant, but the dry mixture was uniform. The dry mixture was mixed using a Haake System 90, 3/4 "conical injector and then injected into the fillet form. The resulting fillet was collected for thin film production.

Table 1A shows typical fillet injection conditions. Thin films are made as follows. The heat resin tube is injected through the first die. The tube is squeezed with a second die to form a film in the thin film with a roller. Then, the injected tube was inflated using the air injected through the air injection tube. The heat resin was dissolved in an injection molding machine. The injection machine temperature is selected in the mixing zone. The melting temperature is selected within the melting point range and the die temperature is selected within the die. The injected resultant is cooled by using the air of the cooling flow which flowed in from the cooling ring. The description below is based on a 40mm diameter die and a Kiefel inflated thin film injection machine used to produce the inflated thin film in practice. Thin films are produced according to the procedures described above, which are reported in Table IB.

The conduction velocity of the thin film was measured under various experimental conditions. The experimental conditions are shown in Table II.

<Table IA>

<Table IB>

Here, ¹ contains 500 ppm of Irganox 1010 antioxidant and 1000 ppm of IrgaFos 168.

<Table II>

² in the table is 7 ppm aromatic permeate and 20 ppm ETOH (ethanol).

<Table II> (continued)

Where 3 is 7 ppm of aromatic permeate and 20 ppm of ETOH (ethanol) and 4 is 40 ppm of naptime.

From the test results, it can be seen that adding a significant amount of cyclodextrin to the thermosetting thin film of the present invention reduces the delivery rate of various infiltrates, thereby substantially improving the barrier function. Data indicating increased delivery rates are shown in the table below.

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The inventors have discovered that a barrier thin film or coating film can be formed from a solution coating composition. Such compositions may be water soluble or used as a solvent. The present inventors produced a series of water-soluble coating films containing hydroxypropyl βCD. One of the coatings was made from a 10% acrylic emulsion (polyacrylic acid polymer having a molecular weight of about 150,000 purchased from Polysciences. Inc.). In this case, the 10% acrylic emulsion contains 5% to 10% of hydroxypropyl βCD by weight. Test thin film samples were prepared by manual coating by stacking two thin films using this solution. The coating was made using a manual roller using a low density polyethylene thin film sheet containing 0.5% acetylated βCD (Roll No. 7) and a second thin film sheet containing 2% acetylated βCD (Roll No. 8). The thin films were then laminated. Vacuum lamination pressure was applied to the coated samples to remove any air bubbles present between the thin sheets. The acrylic coating thickness was about 0.0002 inches (.000051 mm).

Acrylic coated control samples were prepared in the same manner except that hydroxypropyl βCD was not included. The multilayer structure with a 0.5% acetylated βCD thin film was tested with the outer flask face of the test cell facing.

The second coating layer was made of vinylidene chloride latex (PVDC, 69 wt% solids) purchased from Dagax Laboratories, Inc. The PVDC latex coating layer was prepared in two types of 10% hydroxypropyl and 20% based on the weight of the cyclodextrin. These solutions were used to manually coat a low density polyethylene test thin film sample by laminating two thin films. After the coating operation was performed on two control thin sheets using a manual roller, these were laminated. The thin films did not scratch during the lamination process. All coated samples were placed under vacuum lamination pressure to remove air bubbles between the thin sheets. The thickness of the PVDC coating was about 0.0004 inches (.00010 mm).

PVDC coated control samples were prepared in the same manner except that no βCD was added. Such coatings are suitable as cellulosic coatings. This coating is done in a similar manner to thin film coatings. From the following data on the prepared samples, the following general test method shows that the general delivery rate is improved.

Method summary

This method involves an experimental technique designed to measure the permeability of selected organic molecules through food packaging thin films by using constant concentration components. This test technique involves the determination of organic foods previously found in food products that have been previously tested to perform various storage humidity, product water activity and temperature conditions of the product, and to virtually set the organic vapors out of the package within the penetration test cell. By using molecular concentrations, improved storage period test conditions are established virtually.

This method is applicable to compounds such as ethanol, toluene, p-xylene, o-xylene, 1,2,4-trimethylbenzene, naphthalene, naphtha solvent mixtures and the like.

<Table 2>

Three steps are involved in a typical penetration experiment. That is, (a) mechanical precision calibration, (b) thin film test to measure the rate of transfer and diffusion, and (c) qualitative control of the penetration experiment.

Thin film samples are tested with a closed-volume permeation device. High resolution gas chromatography (HRGC) operated with a frame ionization detector (FID) is used to measure the change in total penetration concentration as a function of time. Concentrations of sample and outer test compounds are calculated from the response factors or calibration curves of each compound. Then, if the amount of penetration is desired, the volume is calibrated for each set of penetration cells. The total penetration concentration is shown as a function of time for both the top (outer) and bottom (sample) of the membrane. The diffusion rate and delivery rate of the permeate are calculated from the penetration curve data.

1.0 Equipment and Reagents

1.1 Equipment

Gas Chromatography (HP 5880) with frame ionization detector, 6-port heated sampling valve with 1 ml sampling loop and data integrator

J & W capillary column. DB-5, 30 M × 0.250 mm ID, 1.0 μm df.

Glass permeation cells and flasks. Two glass flasks each having a capacity of about 1200 ml (outer cell or injection side) and a 300 ml capacity (sample flask or penetration side).

Penetration Cell Clamp Ring (2)

Penetration Cell Aluminum Spigot Ring (2)

Natural rubber diaphragm. 8 mm OD reference wall or 9 mm OD (Aldrich Chemical Company, Milwaukee, WI).

Sorting experiment with glass utensils and a syringe.

Classification Experiment Preparation

1.2 Reagents

Reagent water. Water interference is not observed in the MDL of the chemical sample in question. Boil to 80% volume using a water purifier to make reagent water, stopper, and cool to room temperature before use.

Stock ethanol / aromatic standard solution. Packages of ethanol (0.6030 g), toluene (0.1722 g), p-xylene (0.1327 g), o-xylene (0.0666 g), trimethylbenzene (0.0375 g) and naphthalene (0.0400 g) in 1 ml sealed glass ampoules.

Naphtha mixing standards are commercially available colored solvent mixtures comprising about 20 aliphatic hydrocarbon compounds obtained from Sunnyside Corporation, Consumer Products Division, Wheeling, IL.

Triton X-100. Nonylphenol Nonionic Surface Active Reagents (Rohm and Hass)

2.0 Standard Material Manufacturing

2.1 Penetration Test Group Standards

Stock penetration test standard solutions are used.

These standard materials are prepared by measuring the weight of a certified pure reference material that is shown in substantial weight and weight percent.

Experimental ethanol / aromatic standards were prepared by injecting 250 μl of stock standard solution into 100 ml of reagent water containing 0.1 g of surfactant (Triton X-100). Before adding the permeation stock standard, it is important to dissolve the Trition X-100 completely in reagent water. In this way, the test compound can be reliably dispersed in water. In addition, every time a certain amount of dispersion is required to mix the experimental standard materials completely. In order to minimize leakage caused when the upper space of the flask used to prepare the standard material is large, it is preferable to use a crimp-top vial in which the crimp is formed in the form having no upper space at all.

Experimental Naphtha Mixture Standards were prepared by injecting 800 μL of pure naphtha solvent mixture into 100 ml of reagent water containing 0.2 g of surfactant (Trition X-100).

For short-term storage of opened stock standard solution, transfer to a reagent bottle with a crimp top. The reagent bottles are stored in a refrigerator or freezer to prevent explosion.

2.2 Calibration Standards

The calibration standard is placed in the flask and diluted with reagent water to make at least three types of calibration standards. One of the standards has a concentration close to the detection limit but a higher concentration. Other concentrations of standards are made to match the concentration ranges expected in the outer and sample cells.

3.0 Sample Manufacturing

3.1 Thin Film Sample Preparation

The outer flask and the sample flask are washed with soapy water, washed thoroughly with deionized water before use, and dried in an oven. After washing, a rubber diaphragm is placed in each flask.

Using the mold, the thin film test specimen is cut to the inner diameter of the aluminum sealing ring. In order to prevent dispersion losses along the periphery of the cut, it is important to make thin film test specimens with the correct diameter. Assemble the thin film sample, aluminum sealing ring and test flask.

Prepare the test cell. The first sample flask and the outer flask are expanded with dry compressed air to remove moisture in the sample flask and the outer flask. For this purpose, the sample device and the outer diaphragm are drilled using needles and tubes, and dry air is allowed to flow simultaneously in both flasks while controlling the flow rate. Loosen the clamp ring into the flask to prevent pressure buildup on both sides of the membrane. Inject air into both flasks for about 10 minutes, then pull out the needle, tighten the clamp ring and seal between the two flasks with a thin film. Rubber is inserted in the aluminum space to prevent gas from leaking out.

2 μl of water per volume is injected into the 300 ml flask on the sample side. Because the size of the sample flask varies, the amount of water injected depends on the volume change. 2 μl of water per volume injected into the 300 ml flask corresponds to 0.25 activity at 72 ° F. Subsequently, 40 μl of penetrated ethanol / aromatic test group standard or 40 μl of naphtha mixture test group standard prepared in 2.1 is injected into the outer flask. All of these experimental standards had a penetration concentration (ppm-volume / volume) in the 1200 ml flask shown in Table I and exhibited a humidity of 60% at 72 ° F. In the test method, the humidity may be determined using a wet / dry humidity table, and the penetration concentration may be determined from the gas leakage amount, thereby setting other humidity or penetration concentrations. The time is measured and the permeation cell is placed in a controlled oven in thermal parallelism. The sample may be performed at a time difference for convenience in the time required for performing GC. Three identical penetration devices are prepared. Three identical analyzes are performed for QC purposes.

At the end of each time interval, one sample of the group is taken out of the oven. The outer flask is first analyzed using a heated six-port sampling valve held in a 1 ml loop. The loop is inflated with 1 ml volume of outside or sample side air. The loop is injected onto the capillary column. After the injection, the GC / FID system is operated manually. Up to eight 1 ml sample injections can be selected from the sample side and the outside side of a single penetration experiment. Can be performed.

Sample and external test compound concentrations are calculated from the calibration curve or response factor (Equation 1 or 3) of each compound. Then, if the amount of penetration is desired, the volume is calibrated for each particular set of penetration flasks.

4.0 Sample Analysis

4.1 Device Parameters

Standards and samples are analyzed by gas chromatography using the following process parameters.

Column: J & W column, DB-5, 30M, 0.25 mm ID, 1 μm df

Carrier: Hydrogen

Split Ejection: 9.4ml / min

Injection port temperature: 105 ℃

Frame sensor temperature: 200 ℃

Oven Temperature 1: 75 ℃

Program speed 1: 15 ℃

Oven temperature 2: 125 ℃

Speed 2: 20 ℃

Final oven temperature: 200 ℃

Last duration: 2 minutes

The six-port sampling valve temperature was set at 105 ° C.

4.2 Calibration

Three-point calibration was performed using standard materials within the following test compound ranges.

Calibration curve range

<Table>

To prepare a calibration standard, an appropriate volume of experimental standard solution is added to the flask as an aliquot of reagent water.

4.2.1 Second Dilution of Experimental Standard for Calibration Curve

5 to 1 dilution: Into a 25 ml volumetric flask, add 5 ml of the test group standard, stopper, and mix the flask upside down.

2.5 to 1 Dilution: Into a 25 ml volumetric flask, add 10 ml of experimental standard material, stopper and invert the flask upside down.

Each calibration standard is analyzed to tabulate (compound peak area response) versus (concentration of test compound in the outer cell). The results are used to generate calibration curves for each compound. Naphtha solvent mixtures are commercially available colored solvents comprising about 20 aliphatic hydrocarbon compounds. The reaction versus concentration is determined by summing the areas of 20 individual peaks. A straight line to the calibration curve is obtained by the least square method. The slope of the calibration curve is then calculated for each compound to determine the unknown concentration. The mean response factor can be used instead of the calibration curve.

Experimental group calibration curves or response factors can vary from day to day by measuring one or more calibration standard materials. If a compound's response changes by more than 20%, the test should be renewed using a new calibration standard. If the result is still unacceptable, a new calibration curve must be created.

4.3 Analysis of calibration curve and method detection level samples

Preferred chromatographic conditions are summarized above.

As mentioned above, calibrate the system every day.

Check and adjust the split spray rate, and check the speed with a soap film flow meter.

In order to obtain accurate data, samples, calibration criteria, and method sense level samples must be analyzed under the same conditions,

Calibration criteria and method detection samples are prepared only in an external flask. This is done using 1/2 inch (.127 mm) plastic discs and aluminum sheet discs.

The outer glass fringe is closed with one sealing ring, and then an aluminum sheet is installed, on which a plastic disk is placed.

Blow dry air into the outer flask to remove moisture in the outer flask. For this purpose, the outer diaphragm is drilled through the needle and tubular member to control dry air to flow through the flask. The clamp ring is loosely fitted in the flask to prevent the pressure from rising. Air is blown into the two flasks for about 10 minutes, then the needle is removed and the clamp ring is tightened so that the aluminum sheet adheres to the sealing ring.

Subsequently, 40 μl of permeated ethanol / aromatic group standard or a second dilution of the standard is injected into the outer flask. Optionally, 40 μl of a naphtha solvent mixture or a second dilution of the experimental group standard may be injected into the outer flask. Record the time and place the flask in a controlled oven with thermal equilibrium.

After 30 minutes, the outer flask is removed from the oven. The outer flask is analyzed using a heated six-port sampling valve secured with a 1 ml loop. Inflate the loop with 1 ml of outer flask side or sample flask side air. The loop is injected into the capillary column. After injection, the GC / FID system is started manually.

4.4 Correction of Results

4.4.1 Test Compound Reaction Factors

Sample and outer test compound concentrations are calculated for the calibration curve slope or response factor (RF) of each compound.

Then, if appropriate, the concentration is volume-calibrated for each particular pair of infiltrating cells.

The total penetration is shown as a function of time for both the upper flow (outer) and the lower flow (sample) of the membrane. The rate of diffusion and the rate of conduction of the penetration area are calculated from the conduction curve data.

4.4.2 Conduction Speed

If permeation is completely independent of the polymer, the permeability constant R is generally characteristic for permeation-polymer systems. These include the penetration of many gases such as hydrogen, nitrogen, oxygen and carbon dioxide into various polymers. If, as in the case of the test compound used in this method, the penetration is related to the polymer, then P is no longer a constant and will depend on pressure, film thickness and other conditions. In this case, the specific P value will not be representative of the characteristic permeability of the polymer membrane, and knowing the correlation with all possible variables to know the complete permeability profile of the polymer. In this case, when a saturated penetration air pressure is applied to the thin film at a certain temperature, the conduction rate Q is often used for practical purposes. The penetration of thin films into water and organic compounds often appears in this way.

At this time, q represents the following units.

The most critical parameter in determining the penetration factor is the pressure drop across the membrane. Since the unit of conduction velocity does not include the pressure or the concentration of the permeate, it is necessary to know the concentration or air pressure of the permeate under measurement conditions in order to know the correlation of Q to P.

The pressure drop from the outer side to the sample side around the thin film is mainly due to the water vapor pressure. The concentration of water, ie moisture, is not kept constant and is not measured during the time that the organic compound is analyzed, so the pressure across the membrane is not determined.

From the above experiments on thermoplastic resins containing various compatible cyclodextrin derivatives, it can be seen that the present invention can be embodied for various kinds of thermoplastic thin films. In addition, various other kinds of compatible cyclodextrin derivatives may be used in the present invention. Finally, the thin films can be prepared to form useful barriers by various thin film fabrication techniques, such as injection or water soluble dispersion coating.

The above description and experimental examples for substituted cyclodextrins, extruded thermoplastic thin film cellulose network laminates and coated cellulose network laminates and test data are the basic ones for understanding the technical problem of the present invention. The invention can be variously modified within the scope of the appended claims.

Claims (18)

A nonwoven cellulose fiber network having excellent barrier or trap properties against the presence of penetrants or contaminants, (a) a layer comprising a continuous array of randomly arranged cellulose fibers, (b) the non-woven cellulose fiber network comprising a cyclodextrin compound-containing layer, The cyclodextrin-containing layer comprises an amount of cyclodextrin compound effective to absorb permeate, wherein the cyclodextrin compound contains little complex and acts as a barrier to prevent permeate from passing through the outside atmosphere or in the fibrous network. The non-woven cellulose fiber network, characterized in that it serves as a trap for the contaminants generated. The method of claim 1, And wherein said cyclodextrin compound comprises cyclodextrins having at least one pendant or substituent which makes said cyclodextrins compatible with said fibrous network. The method of claim 2, And wherein said cyclodextrin compound comprises at least one substituent at the first carbon position of said cyclodextrin. The method of claim 1, The cyclodextrin is a non-woven cellulose fiber network, characterized in that it comprises α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin or a mixture thereof. The method of claim 2, The cyclodextrin is a non-woven cellulose fiber network, characterized in that it comprises α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin or a mixture thereof. The method of claim 1, The membrane is nonwoven cellulose fiber network, characterized in that it comprises 0.01 to 10% by weight of cyclodextrin. The method of claim 1, And said cyclodextrin compound-containing layer is a coating layer. The method of claim 1, And the cyclodextrin compound-containing layer is a laminated thin film. The method of claim 1, The cyclodextrin is a non-woven cellulose fiber network, characterized in that the acylated cyclodextrin compound. The method of claim 1, The layer comprising a continuous array of disorderedly arranged cellulose fibers has a thickness of at least 0.1 mm, and the cyclodextrin-containing layer is stacked over the layer comprising the continuous array of disorderedly arranged cellulose fibers. The cyclodextrin-containing layer comprises a thermoplastic thin film forming polymer and a modified cyclodextrin compound, wherein the cyclodextrin-containing layer comprises a modified cyclodextrin containing a substituent that makes the cyclodextrin compound compatible with the thermoplastic polymer. A nonwoven cellulose fiber network comprising: The method of claim 10, The laminated network is a non-woven cellulose fiber network, characterized in that it comprises a flexible laminated network. The method of claim 10, Wherein said modified cyclodextrin compound comprises an acetylated cyclodextrin compound. The method of claim 10, And said modified cyclodextrin compound comprises a cyclodextrin having a silicone substituent. The method of claim 10, And the cyclodextrin present in the cyclodextrin-containing layer is present at a concentration of 0.1 to 10% by weight, based on the thermoplastic thin film forming polymer. The method of claim 10, The thermoplastic thin film forming polymer is a non-woven cellulose fiber network, characterized in that it comprises a homopolymer comprising ethylene. The method of claim 10, The non-woven cellulose fiber network, characterized in that the polymer containing ethylene is a copolymer. The method of claim 10,  And the thermoplastic thin film forming polymer comprises a vinyl chloride-containing polymer. The method of claim 1, And wherein said cyclodextrin-containing layer is a stretchable coating layer containing a thin film forming polymer.